Process for producing blended petroleum oil

ABSTRACT

A PROCESS FOR PREPARING A BLENDED PETROLEUM OIL FROM A HYDROGENATED PETROLEUM OIL HAVING AN ULTRAVIOLET ABSORPTIVITY OF LESS THAN 0.1 IN THE 330 MILLIMICRON REGION COMPRISES BLENDING FROM 25-95 PARTS BY WEIGHT OF SAID HYDROGENATED PETROLEUM OIL WITH FROM 75-5 PARTS OF AN UNHYDROGENATED PETROLEUM OIL. PREFERABLY, THE HYDROGENATED PETROLEUM OIL HAS A VISCOSITY-GRAVITY CONSTANT (VGC) IN THE RANGE OF 0.78-0.94 AND THE UNHYDROGENATED OIL HAS A VGC IN THE RANGE OF 0.780.899. THE UNHYDROGENATED OIL CAN BE SELECTED FROM RAFFINATE FROM SOLVENT EXTRACTION OF A NAPHTHENIC DISTILLATE, NAPHTHENIC DISTILLATE, NAPHTHENIC ACID-FREE NAPHTHENIC DISTILLATE, DEWAXED PARAFFINIO DISTILLATE, AND MIXTURES THEREOF. THE HYDROGENATED OIL CAN BE HYDROEREFINED PARAFFINIC PETROLEUM OIL, HYDROREFINED NAPHTHENIC PETROLEUM OIL, HYDROCRACKED PETROLEUM OILS, OR MIXTURES THEREOF. THE BLEND CAN CONTAIN, AS AN ADDITIONAL COMPONENT, FROM 0.1-1 WEIGHT PERCENT OF A CATALYTICALLY CRACKED CYCLE OIL.

PROCESS FOR PRODUCING BLENDED PETROLEUM OIL Filed July 22 1971 April 16, 1974 w, s ETAL 6 Sheets-Sheet 1 ULTRAVIOLET ABSORPTIVITY OF TRANSFORMER OILS WAVELENGTH, MILLIMICRONS m 0 E m F l Mn. E O R 0 m U E ED l M Y F F EH E I P OM RDAA DEXL NYNEI O V TYETA A is; m ma T C m mw FUC oFA V L ZUIO 6S0C 234 \P- n np-h M98765 4 .98755 A 3 2 0987 5 4 3 2 1 100.000. 0 0 0. o

INVENTORS IVOR W. MILLS GLEZNfE. DIMELER E ATTORNEY April 16, 1974 Filed July 22 1971 ABSORPTIVITY AT 335 m/J- l. W. MILLS ETAL PROCESS FOR PRODUCING BLENDED PETROLEUM OIL FIGURE 2 ULTRAVIOLET ABSORPTIVITY AT 335 m NAPTHENIC DISTILLATE HYDROREFIN D AT VARIOUS TEMPERATURES FOR 55 SUS AT lOO F "ACID FREE 335 UVA=O.38 0-63 .06 r so 335UVA 0J6 TOTAL h GEL o 335 UVA D3 I O AROMATICS =o.o7 30 D o h v 0 .02- o 20 UVA AT 335 .Ol no o o P Q HYDROREFINING TEMPERATURE F (0.5 FEED LHSV, 4.0 RECYCLE LHSV; I200 PSIG OF 80 H2) CATALYST: SULFIDED NiMO OXIDES ON ALUMINA INVENTORS IVOR W. MILLS GLENN R. DIMELER ATTOTTIREY 6 Sheets-Sheet 2 TOTAL AROMATIC (ASTM D2057) A ril 16, 1914 NITROGEN AND SULFUR REMOVED PROCESS Filed July 22'. 1971 l. w. MILLS H L v 3,804,743 FOR PRODUCING BLENDED PETROLEUM 01L 6 Sheets-Sheet 3 FIGUREB SULFUR SEVERE- INCREASING REACTION sEVER|TY-- (0.5 FEED LHSV, I200 PSIG OF 80% H MO RECYCLE LHSV INVENTORS IVOR W. MILLS GLENN. R. DIMELER April 16, 1974 w. MILLS ETAL 3,804,743

PROCESS FOR'PRODUCING BLENDED PETROLEUM OIL Filed July 22 1971 6 Sheets-Sheet 4 FIGURE 4 POWER FACTOR x 10 1b HOURS ON TEST (95C WITH AIR,COPPER) INVENTORS IVOR W. MILLS GLENN R. DIMELER Ka w TORNEY April 16, 1974 I w L s ETAL 3,804,743

PROCESS FOR PRODUCING BLENDED PETROLEUM OIL Filed July -22 1971 6 Sheets-Sheet 5 FIGURE 5 O 0.2 0.4 0.6 0.8 L0 L2 POLYNUCLEAR AROMATICS WHICH CONTRIBUTE TO 335 my. UVA

TOTAL ACID NUMBER AFTER 68 HRS. DOBLE OXIDATION TEST CONDITIONS E on Y I. W. MILLS ETA-L April 16, 1974 V PROCESS FOR PRODUCING BLENDED PETROLEUM OIL Filed July 22 ,I 1971 6 Sheets-Sheet 6 FIGURE 6 TOTAL AROMATICS BY GEL O O 0 0 O O O O 0 w W m 5 4 i 2 H m 0 I 5 O I 4 O 1 I 3 O I l 2 m I l o n n 0 O o o O o O 0 O o o 0 o m 7 6 5 4 3 2 mvm 0 SE2 2: $5.95 zQEQxo POLYNUCLEAR AROMATICS WHICH CONTRIBUTE TO 335 UVA INVENTORS IVOR W. MILLS I GLENN R. DIMELER flir United States Patent O 3,804,743 PROCESS FOR PRODUCING BLENDED PETROLEUM OIL Ivor W. Mills, Media, and Glenn R. Dimeler, West Chester, Pa., assignors to Sun Oil Company, Philadelphia, Pa.

Continuation-impart of applications Ser. No. 622,398, Mar. 13, 1967, now Patent No. 3,462,358, Ser. No. 652,026, July 10, 1967, now Patent No. 3,502,567, Ser. No. 730,999, May 22, 1968, Ser. No. 850,716 and Ser. No. 850,717, both Aug. 18, 1969, both now abandoned, Ser. No. 873,008, Oct. 31, 1969, and Ser. No. 22,295, Mar. 24, 1970. This application July 22, 1971, Ser. No.

Int. Cl. C10g 41/00 US. Cl. 208-19 16 Claims ABSTRACT OF THE DISCLOSURE A processfor preparing a blended petroleum oil from a hydrogenated petroleum oil having an ultraviolet absorptivity of less than 0.1 in the 330 millimicron region comprises blending from 25-95 parts by weight of said hydrogenated petroleum oil with from 75-5 parts of an unhydrogenated petroleum oil. Preferably, the hydrogenated petroleum oil has a viscosity-gravity constant (VGC) in the range of 0.78-0.94 and the unhydrogenated oil has a VGC in the range of 0.78-0.899. The unhydrogenated oil can be selected from raffinate from solvent extraction of a naphthenic distillate, naphthenic distillate, naphthenic acid-free naphthenic distillate, dewaxed paraffinic distillate, and mixtures thereof. The hydrogenated oil can be hydrorefined parafiinic petroleum oil, hydrorefined naphthenic petroleum oil, hydrocracked petroleum oils, or mixtures thereof. The blend can contain, as an additional component, from 0.1-1 weight percent of a eatalytically cracked cycle oil.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of all of our applications listed in the following table.

Serial Filing Patent Issue No. date No. date Title 622,398 3-13-67 3, 462, 358 8-19-69 Clay Treatment of Hydrorefined Cable Oils. 652, 026 7-10-67 3, 502, 567 3-24-70 Process for Producing Cable gtils by Sequential Refining eps. 730, 999 -22-68 Hydrorefined Transformer Oil and Process of Manufacture. 850, 716 8-18-69 Blended Hydrocarbon Oil and Process of Manufacture. 850, 717 8-18-69 Hydrorefined Lube Oil and Process of Manufacture. 873, 008 10-31-69 Oil and Process of Manufacture of Blended Hydrorefined Oil. 22,295 3-24-70 Hydrorefined Cable Oil and Process of Manufacture.

1 New abandoned.

In addition to the previously noted patent applications, the following earlier filed copending applications, all assigned to the Sun Oil Company (as is the present application), are related to the disclosure of the present application. The disclosure of all of the following applications 3,804,743 Patented Apr. 16, 1974 and of the above-cited patent applications is hereby incorporated in the present application:

Serial No.

Filing Patent date N o.

Issue date Title Process for Preparing an Aromatic Oil and Non-discoloring Rubber Composition Containing Said Oil-Ivor W. Mills, Glenn R. Dimeler and Merritt C. Kirk, Jr.

High Modulus Composition Comprising Hydrocarbon Oil, Rubber and Carbon BlackIvor W. Mills.

Glenn R. Dimeler, Merritt C. Kirk, In, and Jackson S.

Boyer.

Catalytic Hydrofinishing oi Petroleum Distillates in the Lubricating Oil Boiling Range-Ivor W. Mills, Merritt C. Kirk, Jr., and Albert T. Olenzak.

Process for Preparing High Viscosity Hydrorefined Cable Oil-Ivor W. Mills, Glenn R. Dimeler, William F. Atkinson, and James P. Hoffman.

Electrical Conduit Containing Hydroreflned OilIvor W. Mills, Glenn R. Dimeler and John J. Melchiore.

Light-colored Highly Aromatic Oil and Process of PreparationIvor W. Mills, Glenn R. Dimeler and Merritt C. Kirk, Jr.

5-6-70 Hydraulic Oil Composition Containing a Blended Base Stock-John Q. Griffith, III, Edward S. Williams, William H. Reiland, Jr., Ivor W. Mills and Glenn R. Dimeler.

1 8-3-70 Textile Machinery Lubricant Composition-James R.

Amaroso and John Q.

G -tiith III 9-8-70 Catalytic Hydroflnishing of Lube Oil Product of Solvent Extraction of Petroleum Distillate-Ivor W. Mills, Merritt 0. Kirk, Jr., and Albert 'I. Olenzak.

1 Now abandoned.

The disclosure of all of the above-referred to applications is hereby incorporated herein by reference, particularly as to disclosure therein directed to hydro-refined oils in the lube viscosity range, to uses of such oils, and to the production of such oils.

BACKGROUND OF THE INVENTION The properties of commercial oils used as insulating media in transformers are Well known in the art and a list of typical characteristics is given in the text by F. M. Clark entitled, Insulating Material for Design and Engineering Practice 1962), page 135. Such oils typically boil in the range of 460-775 -F. and have viscosities in the range of 50 to 65 SUS (preferably 55 to 60 SUS) at 100 F., as may be seen by reference to Wasson et al., Pat. No. 3,000,807 and to Wynkoop and Barlett, Pat. No. 3,406,111. There have also been reports of transformer oils having viscosities as low as 40 and as high at 200 SU-S at 100 F. The viscosity gravity constant (i.e. VGC) of the transformer oil can be in the range of 0.82 to 0.92, preferably at least 0.84. The oils of the Wynkoop and Barlett patent are characterized by extremely low total nitrogen content and a very long sludge-free life under the Doble test conditions.

The oils of the present invention can have a total nitrogen content as high at 25 p.p.m. but must have a basic nitrogen content less than 10 p.p.m. (preferably, less than 5 p.p.m., typically less than 1 p.p.m.). They generally have a sludge-free Doble life of less than hours but have good stability under such test conditions as 3 those of ASTM D-13l3 and D943 and have a good impulse breakdown strength. They generally have a VGC in the range of 0.820-0.899 and a viscosity at 100 F. in the range of 40-200 SUS.

A number of processes are known to the art for preparing conventional transformer oils from distillate fractions of naphthenic crude oils. In general, such processes effect the removal of a substantial proportion of the naturally-occurring naphthenic acids and the sulfurand nitrogen-containing compounds which are present as impurities in the naphthenic distillate. A preferred means of removing the naphthenic acid impurities from the distillate is shown, for example, in US. Pats. 2,770,580; 2,795,532; 2,944,014; 2,966,456; and 3,080,312, and can involve conducting the distillation in the presence of a base, such as caustic.

A less preferred method is to remove the naphthenic acid impurity at a later stage in the refining process, such as by contacting with a basic clay in the final finishing or, in the case of hydrorefining, by converting the naphthenic acids to water and the corresponding naphthene (e.g., see The Manufacture of Electrical Insulating Oils by Jennings, H. C. and Lawley, J. R., paper presented to the Edison Electric Institute, Electrical System and Equipment Committees, Sept. 28, 1964, St. Louis, M). The disadvantages of such processes involving removal of the naphthenic acids after the distillation stage are that the naphthenic acids can cause corrosion of equipment and reduce the effectiveness of the treatments for removing other polar compounds, such as the nitrogenand sulfur-containing heterocyclic compounds. In addition, if the naphthenic acids are present in the hydrorefining stage, they are reduced to naphthenes which contain alkyl groups, such as a methyl group, which are susceptible to oxidation to aldehydes or to acids during normal usage in a transformer (e.g., in the presence of copper and oxygen).

One means of preventing such development of oxidation products from naphthenes containing oxidizable alkyl groups is to conduct at least part of the hydrorefining process under conditions (as those shown in the aforementioned Ser. No. 636,493 of Mills, Dimeler and Kirk) such that dealkylation (e.g., demethylation) will occur.

Conventional processes for decreasing the content of heterocyclic sulfur and nitrogen compounds in naphthenic distillate, to produce a transformer oil, involve interaction of such compounds with a reagent, such as hydrogen, which can cause them to decompose to H 8 or NH, and the corresponding hydrocarbon, or involve interaction with a precipitant, such as an acid (e.g., H 80 HF, BF etc.) or involve the use of an adsorbent such as attapulgite and/or an acid-activated clay, or an acidic, crystalline alumino-silicate zeolite adsorbent.

In such conventional processes for refining naphthenic distillate to produce a transformer oil, the proces conditions are usually such that the removal of the sulfurand nitrogen-containing impurities is not selective and the aromatic hydrocarbon content of the distillate is altered by the treatment. In the case of hydrorefining (particularly severe hydrorefining at pressures above about 800 psi. of hydrogen and temperatures above about 500 C., in the presence of catalysts containing cobalt, nickel, molybdenum, tungsten, etc.), the total gel aromatics (such as the tetracyclic and pentacyclic condensed aromatic rings) are altered to a greater extent than are the-less highly condensed aromatic compounds, such as those aromatic compounds which are polynuclear and contain only one aromatic ring.

The conversion by severe hydrorefining (under conditions favoring hydrogenation rather than dehydrogenation) of a polynuclear hydrocarbon having at least four condensed aromatic rings to a polynuclear hydrocarbon containing only one aromatic ring is illustrated by the following (reversible) chemical equations:

H H H H H- H H: H- --H H i H H H H H H /H H I H i I H H H g I I H H H H H Polynuclear Hydrocarbon Having Four Condensed Aromatic Rings (i.e., Tetracyclic Aromatic Hydro- Trlcyclic Aromatic Hydrocarbon Monocyclic Aromatic Hydrocarbon Dicyclic Aromatic Hydrocarbon In the present disclosure, a polynuclear hydrocarbon having four condensed aromatic rings will sometimes be referred to herein as a tetracyclic aromatic hydrocarbon. Similarly, polynuclear hydrocarbons containing one, two or three aromatic rings will be referred to, respectively, as monocyclic, dicyclic and tricyclic aromatics. Note that this nomenclature does not indicate the number of non-aromatic rings in the compounds denoted. Although non-aromatic rings influence the boiling range and fluid properties of the oil, we have discovered that the primary indicator of the oxidation stability (and impulse breakdown strength) of a transformer oil is the aromatic portion of the hydrocarbon, in particular, those aromatic substituents or groupings which contribute to the 335, 330 and 325 UVA of the oil.

Similarly, in the conventional acid treatment of naphthenic distillate to prepare transformer oil the conditions are such that (in order to obtain the desired degree of removal of the polar heterocyclic aromatic compounds in the oil) the total aromatic content of the oil is reduced by as much as 40 to An illustration of the degree of removal of aromatic compounds from naphthenic oils by conventional acid treatment is found in copending United States patent application, Ser. No. 657,438 of Schneider and Stuart, filed May 29, 1967.

We have discovered that in transformer oils produced from a naphthenic distillate by severe hydrorefining, or by conventional acid refining (including acid refining of a raifinate from extraction with an aromatic selective solvent), the content of desired tetracyclic and higher polynuclear aromatic hydrocarbons is such that the oil has an ultraviolet absorptivity at 335 millimicrons of less than 0.04 and that the proportion of such desired polycyclic aromatic compounds which contribute to the 335 UVA compared with less desirable compounds which contribute to the ultraviolet absorptivity at 330 UVA is such that the ratio 335 UVA/330 UVA is less than 1.0. In such oils, the ratio 335 UVA/325 UVA is also less than 1.0 and commonly is less than 0.5. We further discovered (see Ser. No. 730,999) that the sludge-free Doble life of such severely hydrorefined oil can be increased by increasing the content therein of polynuclear aromatic hydrocarbons which contribute to the 335 UVA. One such means is to add a cycle oil, which is rich in such polynuclears, to the severely hydrorefined oil.

For purposes of the present invention, the term 335 UVA denotes 335 rnillirnicronsione millimicron (or the 334-336 mM. region). Similarly, 330 mM. denotes 330: mM. (or the 329-331 mM. region).

SUMMARY OF THE INVENTION The present invention involves our discovery that the performance of such tests as ASTM D-493 and ASTM D-1313 can be greatly increased in a severely hydrorefined naphthenic distillate having a 335 UVA less than about 0.04 (or in the long Doble life oils of application Ser. No. 730,999) if such oils are admixed with raw (i.e. unhydrogenated) naphthenic distillate (preferably naphthenic distillate which is substantially free of naphthenic acids). The unhydrogenated distillate can be a rafiinate from extraction with an aromatic-selective solvent (e.g. furfural, phenol, S0 Prior to blending, the unhydrogenated distillate can be subjected to non-sulfonating acid treatment (to remove basic nitrogen compounds) and/ or can be contacted with an adsorbent (e.g. alumina, activated carbon, attapulgite, Super [Filtrol or the mixtures of US. Pat. 3,369,993). It can be seen herein (e.g., from the examples), however, that an uncracked, nonacid treated, straight-run petroleum distillate (or raflinate thereof) which has not been treated by catalytic contact with hydrogen, is a useful component for blending with hydrogenated petroleum oil.

We have further discovered (see Ser. No. 730,999) that a particularly desirable, novel transformer oil with a Doble life of at least 100 hours and typically at least 20 hours (to as much as 300 hours) has a proportion of desirable tetracyclic and higher polynuclear aromatic hydrocarbons which contribute to the 335 UVA to those less desirable materials which contribute to the 330 UVA such that the ratio of the 335 UVA to the 330 UVA is greater than 1.0. Preferably, when the oil contains less than 25 =p.p.m. of nitrogen and from 25 to 400 ppm. of sulfur, the 335 UV-A can be in the range of 0.06 to 2.0, although oils having a Doble life of 200-300 hours can be prepared having a 335 UVA in the range of 0.3 to 1.0. In such novel oils, the ratio 335 UVA to 325 UVA is commonly about 1.0 (e.g., 0.8 to 1.2).

One means of preparing such a novel transformer oil having a sludge-free Doble life greater than 100 hours is to add a highly dealkylated, highy condensed aromatic hydrocarbon to a severely hydrorefined naphthenic distillate having a 335 UVA less than 0.04. An especially preferred source of such highly dealkylated, highly condensed aromatic hydrocarbons is the recycle (boiling mainly in the range of 600-1000" F. at 1 atmosphere) from the catalytic cracking of gas oil, particularly a gas oil which is cracked in the presence of a cracking catalyst containing a crystalline alumino-silicate zeolite cracking component (see, for example, US. Pat. 3,312,615). For preparing our novel transformer oil, distillate fractions of such catalytically aromatized and dealkylated oils (particularly said recycle stock), boiling mainly in the range of 650-800 F. (more preferably 650-750 F.) are especially desirable' components since their composition is such that the ratio 335 UVA/ 330 UVA is greater than 1.0. The 650-750 F. distillate is also preferred since it will not decrease the flash point or impart a brown or orange visible color to the oil. In general, our novel oils will have a light green fluorescent color and bloom.

Another means of improving the sludge-free Doble life of a severely refined naphthenic distillate having a 335 UVA less than 0.04 is to contact the hydrorefined oil in the presence of a dehydrogenation catalyst (such as sulfided nickel and molybdenum oxides on alumina) under conditions such that the tetracyclic and higher naphthenes and the polynuclear aromatics containing one, two or three aromatic rings in the hydrorefined oil are converted to tetracyclic and higher aromatic compounds, such catalytic contact being conducted at a liquid hourly space velocity (LHSV) of the fresh feed and/or at a recycle LHSV, or combination thereof, such that the resulting aromatized oil has a 335 UVA in the range of 0.04 to 2.5 and, more preferably, in the range of 0.06 to 1.0 (most preferably in the range of 0.15 to 0.4). In such oils, the addition of unhydrogenated naphthenic distillate can improve the D-1313 or D-943 test performance.

To insure proper electrical properties, the oils produced by our process can be contacted with an adsorbent, such as attapulgite or an acid-activated clay (e.g. Super Filtrol), preferably, in the final finishing stage of their manufacture.

By naphthenic distillate, we refer to distillate fractions (or mildly acid treated or solvent raifinates thereof), usually from vacuum distillation, of crudes which are classified as naphthenic (including relatively naphthenic) by the viscosity-gravity constant (VGC) classification method. Typically such crudes are Gulf Coastal and include, for example, Refugio, Mirando, and Black Bayou. The lower VGC oils can be obtained from mid-continental crudes. Such fractions will have a VGC in the range of 0.820 to 0.899 and, usually a viscosity in the range of 40-200 SUS at 100 F. (typically, 50-70). In some cases the crude (and distillate) can have a VGC as high as 0.94. Blends containing such distillates where one (or more) component has a viscosity in the range of 200- 12,000 SUS at 100 F. can also be used where the 'viscosity contributions of all of the components are such that the final blend of hydrorefined and unhydrorefined oil is within the range of 40-200 SUS at 100 F. For products such as textile oils, rubber process oils, refrigerator oils, and most lubricants, the final blend can have a viscosity at 100 F. as high as 1000 SUS, and can contain such components as hydrogenated olefin and/or a hydrocracked lube oil (preferably stabilized by furfural extraction), especially of VI. Such components are described, for example, in US. 3,595,796 and 2,960,458 and in applications Ser. No. 895,302; 78,191 and 90,073.

Examples of such blending are seen in the base oils used for the textile machine oils of Ser. No. 60,642. Base oils for textile oils can advantageously contain unhydrorefined naphthenic distillate and either a solvent refined paramnic lube (which can be hydrorefined), having a VGC of 0780-0819 a hydrorefined naphthenic lube, or a mixture of hydrorefined naphthenic and parafiinic (which can be hydrorefined) lubes, the final base oil generally having an SUS viscosity at F. in the range of 60-600 SUS. Rubber process oils can contain as much as 75% of the unhydrogenated distillate.

BRIEF DESCRIPTION OF THE DRAWINGS In the attached drawings, FIG. 1 illustrates the ultraviolet absorptivity curves which are obtained from transformer oils prepared by various prior art processes and compares them with a novel transformer oil having a long Doble life. In FIG. 1, curve 1 illustrates the UVA curve obtained from a severely hydrorefined naphthenic acid-free, naphthenic distillate which has been clay contacted in the final finishing stage. Curve 2 is that of a sulfuric acid-contacted, furfural raflinate of a naphthenic acid-free, naphthenic distillate which has been contacted with clay in the final finishing stage. Curve 3 is illustrative of a novel transformer oil prepared according to Example H herein. Curve 4 is that of a commercially available hydrorefined transformer oil (which may or may not be prior art) which contains a broad distribution of types of aromatic hydrocarbons and which does not possess the type and distribution of tetracyclic and higher aromatic hydrocarbons as taught in our invention and, thus, has a ratio 336 UVA/ 330 UVA less than 1.0. Note that when oil 3 and oil 4 are compared in the 260 to 330 millimicron region, the shape of the absorptivity curves is very similar, indicating that the materials present in each oil which contribute to absorptivity in this region, are quite similar in nature and proportions. In contrast, in the 330-335 millimicron region the difference in the absorptivity curves is startling and indicates a substantial difference in the composition of the two oils.

In blends of severely hydrorefined and unhydrorefined naphthenic distillates, (where the unhydrorefined component is less than about 13 weight percent of the blend) the UVA curve of the blend will be similar to the UVA curve of the severely hydrorefined component and be generally more comparable in shape to curves 1 and 2 of FIG. I (typically being intermediate in configuration and magnitude).

When such blends contain (as a third component) a cycle oil, the curve of the resulting blend can be similar in configuration to curve 3 of FIG. 1 or if the cycle oil concentration is very low, can be intermediate between curve 1 and curve 3.

FIG. 2 illustrates the eifect of the degree of severity of the hydrorefining conditions on the ultraviolet absorptivity at 335 millimicrons for a feed comprising a naphthenic acid-free, naphthenic distillate. In FIG. 2 the reaction variable which is utilized as an indication of the severity of the hydrorefining is the hydrogenation temperature (in F.). Note that the 335 UVA is at a minimum at about 600 F. and increases at higher temperatures, indicating that dehydrogenation and aromatization are at the higher temperatures. Similarly, the total gel aromatic content of the oil is at a minimum at 600 F. and increases at higher temperatures.

FIG. 3 shows that as the reaction severity increases (as measured by the reaction temperature) the degree of nitrogen and sulfur removal from the oil also increases until (at about 550 F. under the conditions in FIG. 3) over 90% of the nitrogen and sulfur has been removed from the oil. Note that at sutficiently severe hydrorefining conditions essentially all of the nitrogen and sulfur impurities can be removed from the oil.

FIG. 4 shows that the nitrogen content of a naphthenic transformer oil is an indication of the performance of the oil when aged at 95 C. with air in the presence of copper. Therefore, when FIGS. 2, 3 and 4 are considered in combination, they indicate that the reaction severity in hydrorefining should be such that the degree of nitrogen removal is maximized (e.g., with sulfided Ni-Mo catalyst, such as American Cyanamid Co., HDS-3A or HDS-9A, a reaction temperature in the range of 550 650 F., preferably 585-635" F., typically about 600 F., at 0.5 LHSV of fresh feed, 4.0 recycle, 1200 p.s.i.g. of 80% H At this range of hydrorefining severity, FIG. 2 shows that the 335 UVA will be below about 0.01 for a 55 SUS (at 100 F.) feed, thus, indicating that the oil has a very low content of tetracyclic and higher aromatic hydrocarbons which contribute to the 335 UVA. Such low nitrogen, low 335 UVA oils have a very good response to the usual oxidation inhibitors (e.g. the phenolic or amine types) used in transformer oils and, therefore, can be very useful as transformer oils where an inhibitor is permitted. However, when it is desired that the uninhibited oil have a long sludge-free life under the Doble test conditions (i.e., over 64 hours), we have discovered that the hydrorefining conditions should be sufficiently severe as to both lower the nitrogen in the oil to less than 25 p.p.m. (preferably, less than p.p.m.) and also to increase the content of tetracyclic and higher aromatic compounds contributing to the 335 UVA in order that the 335 UVA is greater than 0.04, and preferably at least 0.06. Under the reaction conditions shown in FIG. 2, such an oil having a Doble life of at least 68 hours can be obtained when the reaction temperature is greater than 680 F., and preferably in the range of 685-765 F. If the fresh feed LHSV is less than 0.5, somewhat lower temperatures can be used to achieve the same degree of reaction severity as shown in FIG. 2 (e.g., an oil with a 335 UVA greater than 0.04 can be prepared at 670 F. and 0.25 LHSV). Similarly, at a higher LHSV, a higher reaction temperature is required to obtain this degree of severity. We have found that when hydrotreating with sulfided catalysts prepared from nickel molybdenum oxides or cobalt molybdenum oxides or nickel-cobalt-molybdenum oxides (on the usual carriers, such as alumina), the preferred liquid hourly space velocity of the fresh feed is no greater than 1.0 at hydrogen pressures in the range of 800 p.s.i. to 1600 p.s.i. At higher space velocities kinetic rather than equilibrium conditions occur and the resulting oils tend to be deficient in the desirable polynuclear aromatic hydrocarbons.

FIG. 5 shows the beneficial effect of polynuclear aromatic compounds (which contribute to 335 UVA) on oil stability under Doble oxidation test conditions (here the total acid number after 68 hours of Doble test conditions is used as an indication of oil stability). Note that for an acid number less than about 0.5, the oil must contain at least 0.2% of such polynuclear hydrocarbons containing at least four condensed aromatic rings.

FIG. 6 contains three curves which show the effect of such polynuclear aromatic compounds on oxidation stability under ASTM D-943 test conditions and under the impulse breakdown strength test, a third curve shows the effect of total aromatic content of the oil on the impulse breakdown strength (IBS). Note that this curve is a straight vertical line indicating that aromatics per se do not adversely effect the IBS, but that IBS is highly influenced by the type of aromatic compounds in the oil. An especially good oil for a high IBS can be obtained by extraction of a severely hydrorefined naphthenic lube with an aromatic selective solvent. For example, the raffinate from furfural extraction of a hydrogenated 60 SUS (at F.) naphthentic distillate, has a high IBS and a good inhibitor response (however, the addition of DBPC inhibitor tends to lower the IBS). A blend of 8095% of such a raffinate and 20-5% of unhydrogenated 40-70 SUS naphthenic distillate is also a good transformer oil. The addition of 0.1-1% cycle oil to this blend aids the Doble life.

FURTHER DESCRIPTION OF THE INVENTION In the aforementioned patent application, Ser. No. 652,026, reference is made to our discovery that in the production of transformer oils from a 40-70 SUS (at 100 F.) naphthenic distillate by hydrorefining, it is advantageous to choose conditions (e.g., 625 F., 1200 p.s.i.g. of 80% H such that the sulfur and nitrogen contents of the distillate are substantially reduced and there is a concomitant partial saturation of polycyclic aromatic hydrocarbons such that the ultraviolet adsorptivity of the hydrorefined product at 335 millimicrons (335 UVA) is below 0.04 (preferably below 0.01).

Such severe hydrorefining can be at a temperature in the range of 500 to 750 F. and from 800-3000 p.s.i. of hydrogen partial pressure at a liquid hourly space velocity of from 0.1-8.0, preferably conducted either in vapor phase or trickle phase. Product recycle, for example as in US. 2,900,433, can be used, preferably as a product to fresh feed ratio below 10:1 (more preferably 8:1 to 1:1). Preferably the temperature is below that at which substantial cracking occurs; that is, no more than 20% (preferably less than 10%) of the feed stock is converted to material boiling below 300 F.

Although the maximum hydrorefining temperature which will not produce substantial cracking is somewhat dependent upon the space velocity, the type of catalyst and the pressure, generally it is below 750 F. For severe hydrorefining under non-aromatization conditions, we prefer to operate below 700 F., more preferably below 675 F. At total pressures below 2000 p.s.i.g. and with a fairly fresh catalyst, we prefer a temperature no greater than 650 F. since above that temperature aromatization can occur and/or the production of low boiling material and the degradation of oil viscosity can become substantial. After some months of use, if the activity of the catalyst decreases appreciably, a lower space rate and/or higher temperature (ca. 675" F.) can be used to prolong catalyst life, i.e., to delay regeneration or replacement of the catalyst. FIG. 2 is representative of results which can be obtained during the majority of the catalyst life with HDS-3A catalyst.

Typical of such severe hydrorefining methods, which can be used in our process when conducted within the processing conditions referred to herein, are those of U.S. 2,968,614; 2,993,855; 3,012,963; 3,114,701; 3,144,404 and 3,278,420. It is usual to strip H S from the product and top it (by removing low boiling products) to a desired flash point and/or viscosity.

Typical catalysts are molybdenum oxide, cobalt-molybdenum oxides, nickel-molybdenum oxides, cobaltnickel molybdenum oxides and tungsten-nickel molybdenum oxides, preferably presulfided and on a carrier such as silica, alumina, alumina-titania and alumino-silicates (either crystalline or amorphous). Nickel sulfide, nickelmolybdenum sulfide, tungsten disulfide, nickel-tungsten sulfide and molybdenum disulfide, per se or on a carrier, can also be used as catalysts. Examples of operable catalysts are those of U.S. 2,744,052; 2,758,957; 3,053,- 760; 3,182,016; 3,205,165; 3,227,646; and 3,264,211. A preferred catalyst will permit production of a 100 SUS at 100 F. oil having a 260 UVA of 2.5 or less at about 1000 p.s.i. H 600 F. and 0.5 LHSV.

We prefer that such severe hydrorefining (when under conditions favoring hydrogenation) be a trickle-phase process (although gas-phase operation with hydrogen recycle up to 12,000 s.c.f./B. can be utilized) at 525675 F. and 800 to 1600 p.s.i. of hydrogen partial pressure using a catalyst comprising nickel and molybdenum sulfides on alumina or silica. Usually a cobalt-molybdenum catalyst will require 25 to .100 percent greater hydrogen pressure, at a given temperature, recycle and LHSV, to produce a severely hydrorefined transformer oil comparable to that obtained with a sulfided nickel-molybdenum catalyst.

As has been noted in U.S. 2,973,315, the severity of hydrogenation can be measured by the hydrogen consumption. With a 40 to 200 SUS (more usually 45 to 70 SUS) naphthenic distillate feed, reaction severity can also be followed by observing the change in ultraviolet absorptivity, as in the 260 millimicron region (hereinafter sometimes the 260 UVA). For transformer oil manufacture according to the present invention, the change in absorptivity in the 335 millimicron region (335 UVA) should be observed. That is, due to hydrogenation of polycyclic aromatic hydrocarbons, the resulting hydrogenated oil will have lower (e.g. at least 40%) ultraviolet absorptivity in the 335 millimicron region (and in the 260 mM. region) than will the base oil before hydrogenation. FIG. 2 illustrates the effect of hydrorefining severity on 335 UVA.

Typically, after severe hydrogenation (under non-aromatizing conditions), the 260 mM. absorptivity of the naphthenic distillate is reduced by from 40 to 90% and is less than 5.0 for a 40 to 100 SUS naphthenic distillate feed (more commonly less than 3.5). Preferably, in the 40 to 70 SUS range, the hydrogenated oil will contain less than 0.1% sulfur and less than 25 p.p.m. of nitrogen.

Due to differences in aromatic, sulfur and nitrogen content of the base oils, hydrogen consumption can vary greatly; however, hydrogen consumption for severe hydrorefining of a naphthenic acid-free distillate is usually at least 150 s.c.f./bbl. For an indication of the large hydrogen consumption in severe hydrorefining (under nonaromatizing conditions) see U.S. Pat. 2,973,315 and the aforementioned United States patent application, Ser. No. 622,398. One cause of high hydrogen consumption is that we prefer to hydrorefine at conditions (e.g., 575-650 F., 900 to 1500 p.s.i. of H total pressure 800 to 3000 p.s.i.g., no gas recycle, sulfided Ni-Mo catalyst) such that the total gel aromatics in the feed to the hydrorefining step are reduced by about 5 to 25% (mainly due to removal of polar compounds) and most (55 to of the dicyclic and higher aromatics in the feed are converted to monocyclic aromatics. In particular, under such conditions, the 335 UVA of the resulting severely hydrorefined naphthenic distillate will be less than 0.04.

In contrast, mild hydrogenation processes frequently consume less than s.c.f. of H /bbl. and are characterized by little change in polycyclic aromatic content of the oil (in particular, the 335 UVA after hydrotreating is greater than 0.04 for 40 to 70 SUS naphthenic feed). Mild hydrogenation is frequently termed hydrotreating and is usually conducted below 800 p.s.i. of hydrogen or below 500 F. Typical of mild hydrogenation treatments are U.S. Pats. 2,865,849; 2,921,025; 2,944,015; and 3,011,972.

Although impulse breakdown strength testing is routinely applied to finished transformers (ASA Standard C.57.l2.00-1965), there is a growing tendency to apply this type of testing directly to the transformer oil. A segment of the electrical industry believes that the oil impulse breakdown strengh can influence the impulse breakdown strength of the oil impregnated coil and core structure of the finished transformer.

The test as applied to the oil, uses needle-sphere electrodes with a one inch gap. A 1 /2 x 40 negative wave is applied to the electrodes (as specified in paragraph 8.2.1 of the above-mentioned ASA standard). The breakdown voltages of the oils reported herein are the average of five separate determinations.

Oxidation stability of a transformer oil is improved by reducing nitrogen and sulfur content and by retaining (or returning) polynuclear aromatic compounds which contribute to the 335 UVA and which act as natural inhibitors. Where, however, it is desired to have an impulse breakdown strength in a transformer oil of greater than about 120 kv., such polynuclear aromatics which contribute to the 335 UVA are not desirable. If the hydrotreatment conditions are adjusted such that the resulting hydrorefined oil has a 335 UVA less than about 0.04 the impulse breakdown strength of the resulting severely hydrorefined naphthenic distillate can be as high as kv., as is shown by the curve labelled IBS on the accompanying FIG. 6, which relates impulse breakdown strength to the polynuclear aromatic content of the hydrorefined oil. The percent polynuclear aromatics was determined by measuring the 335 UVA of the oil and comparing it with a calibration curve derived by measurement of the 335 UVA of samples containing known amounts of tetracyclic polynuclear aromatic compounds. In FIG. 6 (and also FIG. 5), a tetracyclic and higher polynuclear aromatic content of 1.01% corresponds to a 335 UVA of 0.15. The calibration curve is linear. At a UVA of 0.45, the polynuclear content is 3% and at a polynuclear content of 0.3% the 335 UVA is 0.045.

Also shown in FIG. 6, is a curve relating the oxidation stability as measured by ASTM Method D-943 to the percent of polynuclear aromatics contributing to the 335 UVA. This curve is labelled D-943 and, when taken in conjunction with the IBS curve on the same figure, shows that in an uninhibited transformer oil prepared from naphthenic distillate it is not possible to maximize both oxidation stability and impulse breakdown strength. However, within the limitations imposed by the laws of physics and chemistry, the curves in the figure can be used by the refiner to enable him to tailor-make an oil having a particular combination of impulse breakdown strength and oxidation stability. That is, the refiner can adjust his refining process (either by choosing aromatizing or nonaromatizing hydrorefining conditions or by blending, as by the addition of polynuclear aromatics to a severely hydrorefined oil) so that the tetracyclic and higher polynuclear aromatic content of the oil (as measured by the 335 UVA) will be such that the desired properties are obtained.

For purposes of the present invention, hydrocracked lubes can be substituted in whole or in part, for hydrogenated (or severely hydrorefined lubes) of the same 100 F. viscosity and VGC if the 335 UVA is as specified herein.

Through the use of conventional oxidation inhibitors, such as 2,6 ditertiary-butyl-p-cresol (DBPC), and the process of the present invention, severely refined transformer oils can be produced which have a maximum impulse breakdown strength and excellent oxidation stability.

In FIG. 6, the nearly vertical straight line represents the impulse breakdown strength as a function of total aromatic content of the oil and demonstrates that total aromatic content does not control impulse breakdown.

We have discovered that transformed oils having excellent color and oxidation resistance can be prepared from severely hydrorefined oils either by the addition thereto of polynuclear aromatic compounds contributing to the 335 UVA or by adjusting the hydrorefining conditions (in a second step or directly from the distillate in one step) such that sufficient hydroaromatization occurs as to convert a portion of the more highly saturated condensed polycyclic hydrocarbons in the oil to more highly aromatic hydrocarbons which contribute to the 335 UVA and which are effective as oxidation inhibitors. We have further discovered that the preferred hydrorefining conditions for severe hydrorefining (whether with or without aromatization) should include a liquid hourly space velocity LHSV) for the fresh feed of no more than 1.0 and preferably no greater than 0.5. This is to be contrasted with the process of US. Pat. 3,252,887, which utilizes an LHSV in the range of 1 to 3, more typically about 2.0.

In general in the present invention, the hydroaromatization of the severely hydrorefined naphthenic distillate will require a temperature above 675 F., a hydrogen pressure below 1600 p.s.i. (and preferably a total pressure below 2000 p.s.i.) and a fresh feed LHSV less than 2.0 (preferably less than 1.0). In addition to the catalysts we have listed as preferred for the severe hydrorefining of naphthenic distillate, in a two stage process involving the hydroaromatization of severely hydrorefined naphthenic distillate, a noble metal catalyst (e.'g., Pt or Ru or Pd on A1 or other dehyrogenation metal catalysts (e.g., Ni on SiO can be used when the sulfur content of the hydrorefined oil is sufficiently low as to not cause catalyst poisoning.

Our preferred conditions for severe hydrorefining wherein aromatization occurs involve a temperature above 625 F. but below the temperature where substantial hydrocracking will occur, a hydrogen partial pressure in the range of 800 to 1600 p.s.i., a total pressure in the range of 1000 to 2000 p.s.i.g. and an LHSV of fresh feed in the range of 0.1 to 1.0, in the presence of a dehydrogenation catalyst, such as a catalyst containing nickel and molyb denum or compounds of these metals. Also operable, but not preferred, are an LHSV below 2.0 and a total pressure as low as 500 p.s.i.g.

The aforementioned US. Pat. 3,252,887, involved blending a high temperature hydrorefined distillate (hydrorefined at a temperature in the range of 630670 F.) with a low temperature hydrorefined distillate (hydro refined at a temperature in the range of SSS-595 F.) wherein the hydrorefined oils are individually prepared by contacting a naphthenic distillate with a hydrorefining catalyst at an LHSV of 1 to 3 and a pressure of 500 to 900 p.s.i.g. We have discovered that highly desirable transformer oils can be prepared by blending from to 85 volume percent of a severely hydrorefined naphthenic distillate having a 335 UVA less than 0.04 (e.g., under the conditions of FIG. 2, the oil hydrorefined at 600 F., and more generally, an oil hydrorefined in the range of 575- 675 F.) with from 85% to 15% of a severely hydrorefined oil having a high 335 UVA (e.g., 0.6 to 1.2) wherein the hydrorefining was conducted under conditions favoring aromatization (preferably, at a temperature in the range of 725800 F., more preferably a temperature in the range of 760-780 F.) and wherein said hydrorefined oils have been individually prepared by contacting a naphthenic distillate (preferably, naphthenic acid free) with a hydrorefining catalyst at an LHSV of the fresh feed of 0.1 to 1.0, a total pressure of 1000 to 2000 p.s.i.g. and a hydrogen pressure in the range of 800 to 1600 p.s.i. The final blended oil, or the individual components thereof, should be contacted with an adsorbent clay, such as attapulgite. Unhydrorefined naphthenic oil can be added to such a blend and/or cycle oil.

As we have noted in our previously cited copending application, Ser. No. 622,398, it is sometimes advantageous in compounding hydrorefined electrical oils to blend the base oil with from 0.05 to 20 volume percent of such additives as chelating agents, viscosity modifiers, synthetic parafiinic oils, hydrotreated oils, acid-treated naphthenic oils and naphthenic distillate (particularly naphthenic distillate which is substantially free naphthenic acids).

Hydrorefining as practiced in our invention can produce oils having product quality which is comparable to and in many cases exceeds that of prior art oils prepared by solvent extraction and/or acid treating. Hydrorefining when compared with acid treating and solvent extraction also possesses the advantages of allowing increased yields and eliminating low quality or troublesome byproducts. In the case of transformer and other electrical oils, the heavy H treating (which produces sulfonates) can be eliminated or be replaced with mild, non-sulfonating acid washing (to remove basic nitrogen compounds, where needed).

Another advantage of our invention is process flexibility in that our process can make a wide variety of products with differing properties from the same naphthenic distillate feed stock. This flexibility is apparent in the curves of FIG. 6, which teach the art how to obtain transformer oils having different values of impulse breakdown strength and oxidation stability.

ILLUSTRATIVE EXAMPLES In the following examples, Example I illustrates the severe hydrorefining of a naphthenic acid free, naphthenic distillate to produce a severely hydrorefined transformer oil having a 335 UVA less than 0.04. This hydrogenated naphthenic distillate can be used as a component of the blends of the present invention.

Example II shows the preparation of a novel, transformer oil (having a long, sludge-free Doble life) by adding to the severely hydrorefined oil of Example I a minor proportion of a distillate fraction of the recycle stock from catalytic cracking of gas oil. Unhydrogenated naphthenic distillate can be added to the product of this example to improve the D-943 or D-1313 performance.

Example III shows the preparation of a transformer oil having a Doble life greater than '64 hours by hydrorefining a naphthenic distillate in a single stage under conditions such that the 335 UVA of the resulting hydrorefined oil is greater than 0.04 and the nitrogen no greater than 25 ppm. Unhydrogenated naphthenic distillate can be added to the product of this example to improve D-943 or D- 1313 performance.

Example IV shows the catalytic aromatization of the severely hydrorefined oil of Example I under conditions such that a portion of a more saturated polynuclear hydrocarbon present in the oil is converted to polynuclear hydrocarbon which contributes to the absorptivity at 335 millimicrons, thereby producing a transformer oil having an increased sludge-free Doble life compared with that of Example I. Unhydrogenated naphthenic distillate can be added to the product of this example to improve D-943 or D-13l3 performance.

Example V shows that hydrorefining conditions can be adjusted such that a transformer oil can be produced by hydrorefining which has a high impulse breakdown strength and a good performance in ASTM Oxidation Test D-1313 but that the sludge-free Doble life of such an oil is not as high as has heretofore been considered desirable in a transformer oil.

Example VI demonstrates that the inhibitor response of transformer oils can differ greatly and that inhibitor response is not necessarily a function of the stability of the uninhibited oil and that unhydrogenated (or raw distillate can be added to improve the D-1313 and/or D-943 performance of various hydrorefined oil or blends of hydrorefined oil and cycle oil (see FIGS. 7, 8 and 9).

EXAMPLE I A naphthenic acid free, naphthenic distillate having a point of 564 F. and a 95% point of 660 F. was contacted with a catalyst prepared by sulfiding a composite of nickel and molybdenum oxides on alumina. The hydrorefining conditions were those shown in FIG. 2 hereof and included 0.5 feed LHSV, 4.0 recycle LHSV,

1200 p.s.i.g. of 80% H and a hydrorefining temperature I of 625 F. After contacting with 10 lbs/barrel of attapulgite, the resulting severely refined transformer oil had a sludge-free Doble life of less than 48 hours. The properties of the feed and product of Example I are shown in Table I hereof.

EXAMPLE II A recycle oil (from catalytic cracking of 450-750 F. gas oil with a catalyst containing 10% of a rare earth exchanged Type Y zeolite in an amrophous aluminosilicate matrix) was distilled to obtain a fraction boiling in the range of 650-750" F. Table II hereof reports the ultraviolet absorptivities at 260, 325 and 335 millimicrons of distillate fractions of the recycle oil.

Two volumes of the 650--750 F. distillate fraction of the recycle oil were blended with 98 volumes of the severely hydrorefined, adsorbent contacted product of Example I. The resulting blending oil had a 335 UVA of 0.35, and the ratio 335 UVA to 330 UVA was greater than 1.0. This blended oil product had an impulse breakdown strength of 110 and a sludge-free Doble life of greater than 150 hours. The ultraviolet absorptivity curve of the resulting blended oil is shown in FIG. 1 as curve 3 and other properties of this oil are reported in Table I as Example H product.

EXAMPLE III Example I was repeated except that the hydrorefining temperature was 750 F. and the feed LHSV 1.0 with no liquid recycle. The resulting oil had a 335 UVA of 0.16, contained 47.4% aromatics, and had a Doble life of 100 hours.

EXAMPLE IV The product of Example I was contacted in a second hydrorefining stage with the Example I catalyst under conditions favoring aromatization (730 F., LHSV 0.5, no recycle, 1200 p.s.i. of 80% hydrogen). The resulting oil had a UVA of 0.2 and a Doble life of greater than 100 hours.

EXAMPLE V Example II was repeated except that the hydrorefining temperature was 552 F., the feed LHSV 1.0, and the pressure, 1200 p.s.i.g. of 100% hydrogen. The resulting oil had an impulse breakdown strength of 162, and a sludge-free Doble life of 48 hours. Properties of the transformer oil produced in this example are listed in Table I as Example IV product.

EXAMPLE VI Although oxidation stability is normally specified by the electrical industry for uninhibited oils, transformer oils usually contain an inhibitor, such as DBPC, when incorporated in a transformer. The inhibitor response of a number of oils was studied by determining the weight percent of DBPC required to allow the resulting inhibited oil to perform satisfactorily at ASTM D-943 test conditions for 500, 1000 and 1500 hours. Table :III reports the result of these studies of inhibitor response and shows that inhibitor response is related to the concentration in the oil of polynuclear aromatic compounds which contribute to the 325 UVA.

The data in Table In demonstrate that all oils do not have a comparable inhibitor response and that inhibitor response is not necessarily a function of the stability of the uninhibited oil. Note that the oils containing the lower percent of polynuclear aromatic hydrocarbons tend to show a higher response to the additive. Oil No. 1 requires approximately 0.2% DBPC to attain 1000 hours life; whereas, Oil No. 4 containing no polynuclear aromatics requires only 0.1% DBPC to provide the same protection. This example shows that the oxidation stability of an oil in the absence of an inhibitor does not necessarily indicate the stability of the oil when inhibited with a given percent of an inhibitor.

98-60 parts by weight of oils such as those of Examples I, III, IV and V can be admixed with from 2-20 parts by weight of raw naphthenic distillate (preferably; free from naphthenic acids) to obtain an oil admixture having improved performance in such tests as ASTM D- 1313 and D-943. Our parent application Ser. No. 850,716, filed Aug. 18, 1969, now abandoned, contained drawings, labeled FIGS. 7, 8 and 9, which illustrated the effect on ASTM Test D-943, impulse breakdown strength, and ASTM Test D-1313 of blending raw naphthenic distillate and hydrogenated naphthenic distillate. These drawings have been transferred to our application Ser. No. 175,775 filed Aug. 27, 1971, which is a continuation-in-part of Ser. No. 850,716. A particularly useful admixture for use as a transformer oil comprises parts by weight of hydrorefined 60 SUS (at 100 F.) naphthenic distillate and 20% raw (unhydrogenated) naphthenic distillate. The resulting blend can also advantageously be finished by adsorbent contacting (e.g. with 10 lb./bbl. of attapulgite) to produce an oil which contains 26% gel aromatics, passes hours of ASTM D- 943 and passes for 70 hours of the Doble Test. Further improvement is observed when 0.03-0.3% of DBPC is added to the clay-finished admixture.

As an alternative to finishing the blend, the unhydrogenated distillate component can be contacted with an adsorbent (e.g. 20 lb. attapulgite per bbl. of oil). The resulting blend contains no more than 1 p.p.m. of basic nitrogen and has a 260 UVA of 1.640, 325 UVA of 0.095 and 335 UVA of 0.026.

Blends of severely hydrorefined petroleum distillate and cycle oil can be useful as reactor coolants and heat exchange fluids. In such fluids the cycle oil component can be, for example, from 10-70 weight percent of the blend and the fluid can also contain unhydrogenated distillate and/or the prior art additives, such as the aromatic ketones of US. 3,009,881. Such blended fluids can be used in the same manner as the fluids of US. 2,883,331; 2,909,487; 2,909,488; 2,933,450; 3,009,881; and 3,331,778.

As an additional component (to hydrorefined oils and unhydrogenated oils) in textile oils or refrigerator oils, high viscosity index hydrocracked oils and/or hydrogenated polyolefin oils (e.g. polybutene) can be used. In the case of the refrigerator oils such blends, of high VI hydrocracked oils, hydrorefined naphthenic oils and unhydrorefined naphthenic oil are the invention of Ivor W. Mills and John J. Melchiore (their concept also being that high VI hydrocracked oil can be substituted in whole or in part for the dewaxed paraffinic component of the blends disclosed in Ser. No. 63,303), see their application Ser. No. 200,185, filed Nov. 18, 1971. Such hydrocracked oils are preferably solvent extracted after hydrocracking and the rafiinate product used as the blending component. The invention claimed is:

Examples of such hydrocracked oils are found in US. '1. Process for preparing a blended petroleum oil from Fat. 3,579,435 and the following commonly-owned appla hydrogenated petroleum distillate oil having an ultracations (the disclosure of which is incorporated herein violet absorptivity of less than 0. 1 in the 330 millimicron by reference): 5 region and consisting essentially of a1 Filing (a) parafiinic petroleum distillate oil having a viscositydate Inventors gravity constant in the range of 0.078-0.8l9 and 780,241..- 11-19-68 Thompson, et 111. now U.S. 3,617,464 issued 11-2-71. which has hydrorefiried; 875,502.. 111069 Thompson. (b) naphthemc petroleum 011 having a v1scos1ty-grav1ty Kressconstant in the range of 820-0 899 and which has t 1. U.s. 3,6 7i 7. 10 90'073 11 16-70 Thompson 6 a new 66 65 Ssued 3o 2 been hydrorefincd, the hydrorefined 011 having an The attached Table IV illustrates a number of blended ultraviolet absorptivity of less than 0.04 in the 335 transformer oils which utihze a solvent extraction step. millimicron region;

TABLE I Properties of transformer oils Example I Example Example Conventional transformer Feed Product product product Viscosity, SUB/100 F.- 57. 2 57.5 57.4 57.9 57.3 57.2 Gravity, API 25. 1 26. 5 26.0 26. 5 25.7 25. 9 Total nitrogen, p.p 74 20 24 23 10 5 Total sulfur, Wt. percent 0.17 0. 04 0. 05 0.05 0. 15 0.05 Aromatics, wt. percent 40 25. 5 27. 3 26. 9 35 32 Performance:

Oxidation ASTM D-943, hours, uninhibited 80 13 204 68 90 Oxidation ASTM D-1313, percent sludge (GE bomb)--- 0. 14 76 0.05 0.06 0. 06-0. 08 0. 06

Impulse breakdown strength, (kv.) 170+ 110 162 152 325 UV A 0.38 0. 05 0. 35 0.083 0.25 0. 17

260 UVA-..- 5.1 1.2 3. 8 1. 48 3. 5 2. 5

Sludge-tree Doble life (hours) 24 48 150+ 48 08 64 1 10 lbJbbl. of 99% H2804 of acid-free naphthenic distillate. R 35 lb.[bbl. of 99% HzSOt treatment 01 turtural rafiinate of acid-free naphthenlc distillate.

TABLE H (c) hydrocracked petroleum distillate oils; or Bolling range and absorptivities of recycle oil from catalytic cracking (d) mlxtures of two or more members from (b) oi450700 F. gas on and (c) above, a

Absorptivitiesatp sa1d process compr1s1ng blendmg from 25-95 parts by Temp. F. welght of sa1d hydrogenated petroleum d1st1llate 011 with at 260 325 335m" from 75-5 parts of an uncracked, non-acid treated PereIengdistilled: straight-run petroleum distillate oil or a raflinate thereof,

10 23%} 1M 1. o 4 said distillate or raffinate having not been treated by cata- 201 616 lytic contact with hydrogen, and recovering said blended i8- 45.2 2.2 1.0 oil without any additional hydrogenation.

40 50- 706 98. 6 m m 2. Process of claim 1 wherem sa1d hydrogenated petro $8- 22 leum oil has a viscosity-gravity constant (VGC) in the so: 794} 118-0 range of 0.78-0.94 and wherein said unhydrogenated oil has a VGC in the range of 0.8200.899. TABLE III 3. Process of claim 1 wherein said unhydrogenated oil Inhibitor response of hydroreflned transformer oils i l ted fro Percent poly. Percent DBPC '(a) raffinate from solvent extraction of a naphthenic nuclear aromatics quired alterdi tillate;

iriio nt D943 life 500 1,000 1,500 naphthenic distillate; 011 number 335 UVA no DBPC hours hours hours (c) naphthen c and-free naphthen c d sullate;

20 240 0,050 0,160 Q35 (d) and dewaxed paraffinic distillate; and, 3'} g g-igg 333 (e) mixtures of two or more members from (a), (b), 010 36 l... 0100 (c) and above- NOTE, 4. Process of claim 3 wherein the blend contains as 011 i l-prepared similarly to Example II Product but with 214% an addltlonal component from welght Percent Of a of the recycle irom a different catalytic cracker. cycle il f l ti ki Oil #2-prepared similarly to Example I Product but at hydroyrefining temperature of 650 F. in order to generate 0.1% poly- Process accordlng to clalm 1 for P p a y on g i g i ggggfigfi figgg Example, carbon oil from a hydrogenated naphthenic distillate hav- Oil t l-prepared similarly to Example 1 Product but at 600 F. ing an ultraviolet absorptlvlty of less than m the 330 TABLE IV Solvent extraction in transformer oil manufacture Oxidation tests, hours Oil No. Base oil Treatment Inhibitor Doble. D943 D1313 1 90% N; 10% 60G Rad (furrural); 10 0 -18, (56), +64.. 118 0. 064

lggltbbi. clay (SF or a 2 60N;10% 60G 85% Ref! (luriural) 0.02% DBPC 64, (72) 3 90% 60N; 10% 60G 85% Rafi (furfural) 0.5% cycle oil 72 (03a experimen 4 90% 60N;10% HT Rafi-.. 00r 10lb./bbl. SF or Atte.. 0.--.- 5 90% 60N;10% HT Rafi.-. None 0.02% DBPC -64, (72l 6 90% SUN; 10% HT Rafl.-. 001' 101bs./bbl. SF or Atta- 0.5% cycle nil NOTE:

"GUN" is hydrorefined naphthenic distillate having viscosity at F. of 60 SUS. 60G" is the raw" distillate which is hydrogenated to make the "GUN". Hf'EhRatg g a rafiinate (85% yield) from luriural extraction (160 F. separation temperature at volume percent turiural dosage based on feed) 0 e 85% Rad (tu rfural)" indicates the ratfinate product of a turfural extraction of the Base Oil at the conditions noted above for ET Rafi". "DEPU is dibutylparacresol inhibitor.

1 7 millimicron region, said process comprising blending from 75-95 parts of said hydrogenated naphthenic distillate with from 5-25 parts of uncracked, non-acid treated, straight-run naphthenic distillate which has not been treated by catalytic contact with hydrogen.

6. Process according to claim 5 wherein said naphthenic distillate is substantially free of naphthenic acids.

' 7. Process according to claim 6 wherein said nonhydrogen contacted, straight-run naphthenic distillate has an ultraviolet absorptivity at 260 millimicrons in the range of 1.0-6.0.

8. Process according to claim 7 wherein said nonhydrogen contacted, straight-run naphthenic distillate has an ultraviolet absorptivity at 330 millimicrons in the range of 0.05-2.0.

9. Process for preparing a hydrocarbon oil of improved stability from a severely hydrorefined naphthenic petroleum distillate oil having a viscosity from 40 to 200 SUS at 100 F., a viscosity-gravity constant in the range of 0820-0899, and having an ultraviolet absorptivity of less than 0.04 in the 335 millimicron region, said process comprising the steps of:

(a) increasing the content of said hydrorefined oil of polynuclear hydrocarbons having at least four condensed aromatic rings until said absorptivity at 335 millimicrons is from 0.04 to 2.5;

(b) admixing 225 parts by weight of unhydrorefined, uncracked, non-acid treated naphthenic acid-free straight-run naphthenic distillate with from 98-75 parts of said hydrorefined distillate prior to said step (a) or of the resulting oil of step (a); and

(c) recovering said blended oil Without any additional hydrogenation.

10. The process of claim 9 wherein the resulting oil admixture or the naphthenic distillate component is contacted with an adsorbent and the product of the process is a transformer oil having a sludge-free Doble life of at least 64 hours.

'11. Process according to claim 9 wherein said content of polynuclear hydrocarbons having at least four condensed aromatic rings is increased by converting at least a portion of a more saturated polynuclear hydrocarbon 18 present in said severely hydrorefined oil to a polynuclear hydrocarbon which contributes to the absorptivity at 335 millimicrons and has at least four condensed aromatic Ill'lgS.

'12. Process according to claim 9 wherein said content of polynuclear hydrocarbons having at least four condensed aromatic rings is increased by adding to the hydrorefine d oil or to a blend of the hydrorefined oil and the naphthenic distillate, an oil which is rich in said polynuclear hydrocarbons.

13. Process according to claim 12 wherein said oil rich in said polynuclear hydrocarbons boils mainly in the range of 600-1000 F. and is a recycle stock obtained from catalytic cracking of gas oil.

14. Process according to claim 9 wherein said unhydrorefined straight-run distillate has been distilled in the ,presence of a base to remove naphthenic acid impurities from the distillate.

15. Process according to claim 1 wherein said hydrogenated petroleum distillate oil is a mixture of two or more members from said groups (a), (b) and (c).

16. Process according to claim 1 wherein one or more of the component oils of said blend has a viscosity at F. in the range of 200-12,000 SUS and wherein said blended oil has a viscosity in the range of 40-200 SUS at 100 F.

References Cited UNITED STATES PATENTS 2,288,373 6/ 1942 Smith et al. 20814 3,145,161 8/1964 Anderson et al. 20814 3,252,887 5/1966 'Rizzuti 20814 3,000,807 9/1961 Wasson et al. 20814 3,419,497 12/1968 'ROcchini et al 208-19 3,619,414 11/1971 Mills et al. 20814 3,196,102 7/1965 Mills et al. 20814 2,846,372 8/ 1958 Schneider et al. 20814 3,318,799 5/1967 Acker et al 20814 HERBERT LEVINE, Primary Examiner US. Cl. X.R. 20814 

